Liquid fuel and method of producing same



' medium.

I Patented Apr. 1946 I UNITED STATES PATENT OFFICE 2,397,859 mourn rum. Ami sm'rnon or raonncmo Arthur B. Bersbei-ger, Drexel Hill, and Kenneth M. Thompson, Aidan, Pa., asslgnors Atlantic Refining Company, Philadelphia, 7a., a corporation of Pennsylvania No Drawing. Application March 20,1943,

Serial No. 479,951

in the manufacture of composite fuel from coal and oil, such fuel being of the type in which coal or other bituminous material, in a fine state of division, is maintained in suspension in an oil In accordance with the presentinventiom coal or the like in a fine state of division is suspended inhydrecarbon oil, and such suspension is stabilized b the incorporation of a small amount of an acidic compound such as an organic or inorganic acid or derivative thereof. In producing the suspension, it has been found that most satisfactory resultsare obtained by pulverizing the coal or other bituminous material in the presence of a small amount of the acidic stabilizing agent,

Cl. 44-51) used in the polymerization of hydrocarbons "such as gaseous oleflns, or which has been useddn the alkylation of isoparamns with olefins or aromatics with olenns,-and which ma contain hydrocarbon sulfates or phosphates may be suitably employed in accordance with this invention. Organic sulfohicacids or sulfuric acid sludges containing sulfonic acids resulting from the treatment of hydrocarbon oils with sulfuric acid,-

oleum, or sulfur trioxide may also be ,utillud as stabilizing agents. The quantity of acid stabilizer used may range from about 0.1% to 5% based upon the total composite fuel produced. quantities and thereafter incorporating this mixture in hydrocarbon' oil of the nature of fuel oil,

' The bituminous materials which may be uti-- of the orderv of 0.5% to 1.5% being preferred.

In producing the suspension of bituminous material in oil, we have found that most satisfactory results are obtained by adding to the bituminous material during the pulverizing operation, the desired quantity of acid stabilizer so that such m stabilizer may be thoroughly distributed in and over the surfaces of the bituminous particles.

-' The pulverizing of the bituminous material and the addition of the acid stabilizer thereto may be carried out in a suitable apparatus such as of coal or petroleum. The hydrocarbon oils a grinder or ball mill or Raymond mill, and the which may be employed as the liquid mediav are exemplified by relatively high boiling distillates of crackedor uncracked petroleum, oal tar, petroleum tar, residues from the polymerization of hydrocarbon gases and oils, oils or oil fractions from the destructive hydrogenation of coal or petroleum, and heavy residual oils from the refining of petroleum. The bituminous materials are pulverized to pass 100 mesh, and preferably 200 mesh, it having been found that the finer the state of division, the more readily. the suspension is stabilized. The proportion of pulverized bitu-" minous material to oil may vary from-about 10% to 60% by weight of the oil, a ratio of 40 parts may also be produced by first distributing the stabilizer in the oil and thereafter incorporating the finely divided bituminous material, or by admixing the bituminous material, stabilizer, and oil simultaneously. However, the methodflrstde scribed aboveis Preferred.

of bituminous material to parts ofoil being 40 preferred. y

The stabilizing agents which may be employed include sulfuric acid of from to con-.- centration, a concentration of, from 93% to 98% being preferred. Spent sulfuricacid from the treatment of hydrocarbon oils which has been Our invention maybe further illustrated bythe followingexamples, which, however, are not to be construed as limiting the scope thereof. In these examples, the acid stabilizing agent was distributed uniformly through the pulverized coal 45 by thorough milling in a ball mill. The resultin recovered and reconcentrated may be used, as

may the sludge orsludge acids in which the sulfuric acid has-a concentration of'at least 80%.

mixture was dispersed in a hydrocarbon fuel oil having a Furol viscosity of 56 seconds at 122' F. and an A. P. I. gravity of 14'. by feeding the mixture into the oil with vigorous agitation until Sulfuric acid or phosphoric acid which has been so a homogeneous suspension was obtained. A puland the amount of acid stabilizer used was based of sulfuric acid, hydrocarbon sulfonic acids, and

phosphoric acid.

upon the total compositefuel, i. ,e., coal plus oil.

The stability of the composite fuel was determined bypermitting samples to stand in a quiescent. state and noting the number of days required to obtain settlement of 30% of the coal initially incorporated in the oil.

' Stability Coal Weight,

mam Acid stabilizer percent Tem O Days 150/200 None"-.. 77 7. 5 150/200 Sulionic acids from gas Oil acid sludge 1. 77 12. 150/200 Sulfuric acid (98% conc.) 1. 0 77 65. 0 200/250 None 120 4. 5 200/250 Sulfonic acids from gas oil acid sludge 0. 5 120 9.0 200/250 Diiso ropyl benzene sulion c acids 0. 5 120 25.0 200/250 Sulfuric acid sludge from manufacture of medicinal white oil 1. 5 120 62. 0 200/250 Sulfuric acid (98% conc.) 0. 5 120 I 34. 5 200/250 ----do l. 5 120 68. 0

tration, and this stabilizer is preferred since it is relatively inexpensive and readily available.

We claim: f 1. A method of producing a stable suspension of finely divided bituminous fuel in hydrocarbon oil, which consists in incorporating a small quantity of a-sulfonic acid in said finely divided bituminuous fuel, and dispersing'said fuel-in hydrocarbon oil. v

= 2. A method of producing a stable suspension of finely divided bituminous fuel in hydrocarbon oil, which consists in incorporating a small quantityof petroleum sulfuric acid sludge in said finely.

divided bituminous fuel, anddispersing said fuel in hydrocarbon oil.

8. A'method of producing a stable suspension of finely divided bituminous fuel in hydrocarbon oil,

which consists in intimately mixing said finely divided bituminous fuel with said hydrocarbon oil and a small but sufilcient quantity of an acid from the group consisting of sulfuric acid, hydrocarbon divided bituminous fuel with said hydrocarbon 10. A method of producing a stable suspension offinely divided bituminous fuel in hydrocarbon oil, which consists in intimately mixing said finely divided bituminous fuel with said hydrocarbon oil and from 0.5 per centto 1.5 per cent of an acid from the group consisting of sulfuric acid, bydro-' carbon sulfonic acids, and phosphoric acid to stabilize said fuel in said oil.

11. A method of producing a stable suspension of finely divided bituminous fuel in hydrocarbon oil, which consists in incorporating a small quan- 3. A liquid fuel consisting of a sulfuric acidstabilized suspension of finely divided bituminous fuel in hydrocarbon oil. 4.'A liquid fuel consisting of a suspension of finely divided bituminous fuel in hydrocarbon oil and a small quantity of sulfuric acid sufficient to stabilize said suspension.

- 5. A liquid fuel consisting of a suspension of finely divided coal in hydrocarbon oil and from 0.1% to 5% of sulfuric acid incorporated in said suspension.

6. A liquid fuel consisting of a suspension of. finely divided coal in hydrocarbon oil and from 0.5% to 1.5% of sulfuric acid incorporated in said suspension.

7. A liquid fuel consisting of asuspension of finely divided bituminous fuel in hydrocarbon oil, 6

tity of an acid from the group consisting of sulfuric acid, hydrocarbon sulfonic acids, and phosphoric acid in said finely divided bituminous fuel. 'and dispersing said fuel in hydrocarbon oil.

' 12. A method of producing a stable suspension of finely divided bituminous fuel in hydrocarbon oil, which consists in incorporating a small quantityof acid from the group consisting of sulfuric acid, hydrocarbon sulfonic acids, and phosphoric acid in said hydrocarbon oil, and dispersing said finely divided bituminous fuel in said hydrocarbon oil.

.13. A method of producing .a stable suspension of finely divided bituminous fuelin hydrocarbon oil, which consists in .pulverizing saidfuelin the presence of a small quantity of an acid from the group consisting of sulfuric acid, hydrocarbon sulfonic acids, and phosphoric acid, and dispersing said finely divided bituminous fuel-in-hydrocarbon oil.

14. A method of producing a stable suspension of finely divided bituminous fuel in hydrocarbon oil, which consists in incorporatinga small quantity of sulfuric. acid in said finely divided bitu- 16. A liquid fuel consisting of a suspension of finely divided coal in hydrocarbon oil and from 0.1% to 5% of a petroleum sulfuric acid sludge incorporated in'said suspension.

ARTHUR B. 'HERSHBERGER. KENNETH M. THOMPSON. 

